JP2016536287A - Ether amines and their use as curing agents or intermediates for polymer synthesis - Google Patents

Abstract

The examples described herein are generally ether ether amines formed from mixtures of two or more polyfunctional alcohol initiators, processes for making ether amine mixtures, and as curing agents or raw materials in the synthesis of polymers. Related to its use. In one embodiment, the method mixes a polyol initiator having a melting point above the processing temperature and a polyol initiator having a melting point below the processing temperature to form a polyol initiator mixture having a melting point below the processing temperature. Filling the alkoxylation reaction zone with a polyol initiator mixture, contacting the polyol initiator mixture with an alkylene oxide in the alkoxylation reaction zone to provide a mixture of alkoxylated precursor polyols, and alkoxylation Filling the mixture of precursor polyols into the reductive amination zone and reductively aminating the mixture of alkoxylated precursor polyols to form an ether amine mixture.

Description

  The examples described herein are generally used as ether amine mixtures formed from mixtures of two or more multifunctional alcohol initiators, processes for making ether amine mixtures, and as curing agents or as raw materials in polymer synthesis. Its use.

  Polyoxyalkylene amines or “polyether amines”, as they are sometimes referred to, are useful as curing agents in epoxy systems to improve flexibility and extend the working time in the manufacture of fiber reinforced composites. is there. Polyether amines are generally produced by reaction of alkylene oxides with alcohols to form polyoxyalkylene polyols, after which the hydroxyl groups are subsequently converted to amine groups by reductive amination. For example, Patent Document 1 describes a method in which a polyoxyalkylene polyol is treated with ammonia and hydrogen in the presence of nickel oxide, copper oxide and chromium oxide catalyst to form a mixture of polyetheramines (patent). Reference 1). Patent Document 2 further describes a method in which a polymer polyoxyalkyleneamine is produced by contacting a polymer polyoxyalkylene polyol with ammonia in the presence of hydrogen and a Raney nickel / aluminum catalyst (Patent Document 2). 2). In addition, US Pat. No. 6,057,049 discloses a process in which propoxylated 1,4-butanediol is first aminated using a Raney nickel catalyst and then converted to an adduct by reaction with a small amount of epoxy resin. (See Patent Document 3). Finally, Patent Document 4 describes a method for producing hindered polyether diamines and polyether triamines by reductive amination of various polyoxyalkylene polyols (see Patent Document 4).

  In some methods of making polyether diamines, the alcohol precursor used for alkoxylation is typically a liquid at room temperature or a solid raw material with a low melting point. Due to the high energy consumption and the need for more capital investment to add heat tracking capability, raw materials with higher melting points are typically excluded from modern methods. These high melting raw materials sometimes have individual characteristics such as a hard backbone, high functionality and the like.

  Accordingly, there is a need for an improved process for producing ether amine mixtures from two or more multifunctional alcohol initiators, wherein at least one of the multifunctional initiators is an alcohol having a higher melting point. Exists.

US Pat. No. 3,654,370 US Pat. No. 4,766,245 U.S. Pat. No. 4,769,438 US Pat. No. 7,550,550

  The practice described herein is generally as an ether amine mixture formed from a mixture of two or more polyfunctional alcohol initiators, a method of producing an ether amine mixture, and as a curing agent or as a raw material in the synthesis of polymers. Related to its use. In one implementation, a method for preparing an etheramine mixture is provided. The process comprises: (a) mixing a first polyol initiator having a melting point higher than the processing temperature and a second polyol initiator having a melting point lower than the processing temperature to start a polyol having a melting point lower than the processing temperature. (B) filling the alkoxylation reaction zone with the polyol initiator mixture in the presence of an alkali metal hydroxide catalyst; (c) alkylene in the alkoxylation reaction zone with the polyol initiator mixture. Contacting the oxide to provide a mixture of the alkoxylated precursor polyol, and (d) charging the reductive amination zone with the mixture of the alkoxylated precursor polyol and in the presence of the reductive amination catalyst and ammonia. , Reductively aminating a mixture of alkoxylated precursor polyols to form an ether amine mixture Comprising a.

  In other implementations, a composition comprising an etheramine mixture is provided. The ether amine mixture comprises the reaction product of ammonia and an alkoxylated precursor polyol mixture, where the reaction is carried out under reductive amination reaction conditions, the alkoxylated polyol mixture having a melting point below the processing temperature. And the alkylene oxide reaction product, wherein the polyol initiator mixture comprises a first polyol initiator having a melting point above the processing temperature and a second polyol initiator having a melting point below the processing temperature.

  In yet another embodiment, a composition is provided. Its composition is

[Wherein L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene, preferred Are C ₄ -C ₈ cycloalkylene and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene and preferably C ₂ -C ₄ alkylene-C _5-. C ₆ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₂ -C ₄ alkylene and preferably C ₂ -C ₄ alkylene-C ₅ -C ₆ cycloalkylene-C ₂ -C ₄ Alkylene, R ₃ and R ₄ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or molecular C ₂ — C ₅ alkenyl group, or If may be substituted or unsubstituted C ₆ -C ₁₂ aryl, and at least one of the m and n is 1 or more, it m and n are each individually a number of 0-6 Can do]:
Comprising.

  In yet another embodiment, a composition is provided. Its composition is

[Wherein R ₅ and R ₆ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and m + n is equal to a non-zero integer between 1 and 6]:
Comprising.

  The practice described herein is generally an ether amine mixture formed from a mixture of two or more multifunctional alcohol initiators, a method for producing an ether amine mixture, and as a curing agent or as a raw material in the synthesis of polymers. Related to its use. More specifically, the practice described herein generally relates to etheramine mixtures formed from at least two multifunctional alcohol initiators, at least one of which is a high melting point polyol. .

  Some implementations described herein further include from a mixture of an alkylene oxide (eg, ethylene oxide (EO), propylene oxide (PO) or butylene oxide (BO)) and two or more multifunctional alcohol initiators. Relates to the synthesis of amine-terminated compounds, followed by further reductive amination. Amine-terminated compounds have improved thermal stability, increased glass transition temperature, and in some implementations can be used to produce products with slower amine reactivity. Such products are useful in curing epoxy composite binders, particularly those used in the manufacture of wind turbine generator blades. The implementations described herein further provide several processing methods for preparing compositions of the aforementioned materials.

  The implementation described herein further includes the synthesis of new compositions of materials that are ether amines with significant amounts of oligomers with a very limited amount of oxygen atoms in the oligomer backbone. Some implementations described herein further provide significantly improved thermal resistance and longer for large blade applications as measured by glass transition temperature when used to cure epoxy resins. Provides high thermal stability and delayed amine reactivity, allowing epoxy systems with open times.

  In some implementations, to produce such ether amines, an alkylene oxide is added to a mixture of two or more multifunctional alcohol initiators to form a mixture of alkoxylated polyols. These intermediate polyols then undergo reductive amination. The crude reaction product is then stripped of ammonia and water to provide a final mixture of amine products, which can then be analyzed for amine conversion, water content and oligomer mixing ratio.

Using the implementation described herein, the molecule contains a hard, hindered structure, a light color (l
high yields of multifunctional amines with low color) and low viscosity. Suitable multifunctional alcohol-based initiators include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, ethylene glycol, and combinations thereof.

  These mixtures of polyfunctional amines described herein can be used as intermediates in a number of polymer forming applications. These mixtures can also find use as components of epoxy hardeners to provide high thermal stability to structural composites or molding materials. These mixtures can also be useful for adhesives and coatings of various industrial materials. Some of these products can be used to prepare polyurea and thermoplastic polyamide materials.

  In some implementations, a method is provided for preparing an etheramine mixture as described herein. The method comprises: (a) mixing a first polyol initiator having a melting point higher than the processing temperature with a second polyol initiator having a melting point lower than the processing temperature to start a polyol having a melting point lower than the processing temperature. A step of forming an agent mixture, (b) a step of filling the alkoxylation reaction zone with a polyol initiator mixture in the presence of an alkali metal hydroxide catalyst, and (c) a polyol initiator mixture within the alkoxylation reaction zone. Contacting the alkylene oxide to provide a mixture of alkoxylated precursor polyols, and (d) charging the mixture of alkoxylated precursor polyols into the reductive amination zone and in the presence of the reductive amination catalyst and ammonia. The reductive amination of the mixture of alkoxylated precursor polyols to form an ether amine mixture Degree: comprises a.

  In some implementations, a first polyol initiator having a melting point above the processing temperature is mixed with a second polyol initiator having a melting point below the processing temperature to provide a polyol initiator mixture having a melting point below the processing temperature. Form. The first polyol initiator can be a high melting point initiator. The first polyol initiator can be a solid, semi-solid, or a combination thereof at the processing temperature. The second polyol initiator can be a low melting point initiator. The second polyol initiator can be a liquid at the processing temperature. The first polyol initiator and the second polyol initiator can each individually be a diol. The first polyol initiator and the second polyol initiator are each individually of formula (I):

Can be selected from polyols based on

In the formula (I), L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene Preferably C ₄ -C ₈ cycloalkylene and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene and preferably C ₂ -C ₄ alkylene-C; ₅ -C ₆ cycloalkylene; C ₂ -C ₄ alkylene -C ₃ -C ₁₂ cycloalkylene -C ₂ -C ₄ alkylene and preferably at C ₂ -C ₄ alkylene -C ₅ -C ₆ cycloalkylene -C ₂ - It can be C ₄ alkylene.

The first polyol initiator can include a polyol initiator that is solid or semi-solid at the processing temperature. A suitable first polyol initiator includes neopentyl glycol. The first polyol initiator has a melting point above 60 ° C, above 70 ° C, above 80 ° C, above 90 ° C, above 100 ° C, above 110 ° C, above 120 ° C and above 130 ° C. be able to.

  The second polyol initiator can be liquid or semi-solid at the processing temperature. Suitable second polyol initiators include, but are not limited to, 1,4-cyclohexanedimethanol, 1,4-butanediol, ethylene glycol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 2,2,4-trimethyl-1,3-pentanediol, hexanediol, trimethylolpropane, triethylolpropane, pentaerythritol, cyclobutanediol, cyclopentanediol, cyclohexanediol, cyclododecanediol, and combinations thereof including. The second polyol initiator typically has a melting point that is lower than the melting point of the first polyol initiator. The second polyol initiator is below 100 ° C, below 90 ° C, below 80 ° C, below 70 ° C, below 60 ° C, below 50 ° C, below 40 ° C, below 30 ° C, above 20 ° C Can have a low melting point, lower than 10 ° C and lower than 0 ° C.

  In some implementations, the melting point of the second polyol initiator mixture is lower than 60 ° C and the melting point of the first polyol initiator is higher than 60 ° C.

  In some examples, the weight ratio of the first polyol initiator to the second polyol initiator in the polyol initiator mixture is about 10:90 to 90:10.

  After filling the polyol initiator mixture into the alkoxylation reaction zone, the polyol initiator mixture is then contacted with the alkylene oxide in the alkoxylation reaction zone for a period of time sufficient to provide a mixture of alkoxylated polyols. The alkylene oxide has the formula (II):

Can be an alkylene oxide.

In formula (II), R ₁ and R ₂ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₆ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group may be a substituted or unsubstituted C ₆ -C ₁₂ aryl,. The alkylene oxide is preferably ethylene oxide, propylene oxide, butylene oxide (such as isobutylene oxide, 1,2-butylene oxide and 2,3-butylene oxide), pentylene oxide, styrene oxide or combinations thereof. The amount of alkylene oxide contacted with the mixture of polyol initiators can range from about 0 to 5 moles, preferably from about 0.5 to 2 moles of alkylene oxide per mole of polyol initiator. The period during which the initiator is contacted with the alkylene oxide is sufficient to form a mixture of alkoxylated polyols, and in some embodiments is in the range of about 0.5 hours to about 24 hours. Can do.

  In one embodiment, the alkoxylation reaction zone is a closed reactor and the alkoxylation is carried out at elevated temperature and pressure and in the presence of a base catalyst. Thus, alkoxylation can be carried out at processing temperatures in the range of about 50 ° C to about 150 ° C. Processing temperature is higher than 50 ° C, higher than 60 ° C, higher than 70 ° C, higher than 80 ° C, higher than 90 ° C, higher than 100 ° C, higher than 110 ° C, higher than 120 ° C, higher than 130 ° C, 140 ° C It can be higher or higher than 150 ° C. Alkoxylation can be carried out under pressures ranging from about 40 psi to about 100 psi. The base catalyst may be any alkaline compound commonly used in base-catalyzed reactions, for example, alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide or cesium hydroxide, or dimethylcyclohexylamine or 1,1, It can be a tertiary amine such as 3,3-tetramethylguanidine. After alkoxylation, the unreacted oxide can be stripped and the resulting mixture can be neutralized with magnesium silicate (ie, Magnesol®). The reaction mixture can then be stripped to remove any light reactants and water, and then the filtered alkoxylated polyol can be recovered.

  The mixture of alkoxylated polyols has the formula (III):

Based on at least one alkoxylated polyol.

In formula (III), R ₃ and R ₄ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group or a substituted or unsubstituted C ₆ -C ₁₂ aryl, can be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. m and n can each be 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6 when at least one of m and n is 1 or more. The sum of m + n can be between 1 and 12, for example, the number 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene, and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene, preferably C ₄ -C ₈ cycloalkylene and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene -C ₃ -C ₁₂ cycloalkylene and preferably at C ₂ -C ₄ alkylene -C ₅ -C ₆ in C ₂ -C ₄ alkylene -C ₃ -C ₁₂ cycloalkylene -C ₂ -C ₄ alkylene and preferably at C ₂ -C ₄ alkylene -C ₅ -C ₆ cycloalkylene -C ₂ -C ₄ alkylene; cycloalkylene Can be.

The mixture of alkoxylated polyols can then be used as a feed for the reductive amination stage. Since the addition during the alkoxylation period is random, the mixture of alkoxylated polyols formed in the alkoxylation reaction zone is not a pure compound, but rather a mixture of unreacted initiator and monoether and polyether polyols. It is thought that. The proportions of these polyols vary considerably and can be led to the formation of monoether polyols by adjusting the ratio of alkylene oxide to initiator in the alkoxylation reaction zone. Thus, in some implementations, the mixture of alkoxylated polyols is at least 10% by weight, preferably at least 20% by weight, more preferably at least about 30% by weight, based on the total weight of the alkoxylated polyol mixture, and Even more preferably, it will contain at least about 40% by weight of the monoether polyol. In some implementations, the alkoxylated polyol mixture is about 10 wt% to about 70 wt%, preferably about 20 wt% to about 60 wt%, and more based on the total weight of the alkoxylated polyol mixture. Preferably it will contain from about 30% to about 50% by weight monoether polyol.

  In some implementations, prior to reductive amination, the mixture of alkoxylated polyols is neutralized using any suitable acid or chemical adsorbent, such as, for example, oxalic acid or magnesium silicate, and insoluble materials. Can be filtered for removal. The mixture of alkoxylated polyols is then charged to the reductive amination zone where it is contacted with a reductive amination catalyst, sometimes referred to as a hydrogenation-dehydrogenation catalyst, under conditions of reductive amination and ammonia. Reductively aminated in the presence of hydrogen. Reductive amination conditions can include, for example, a temperature in the range of about 100 ° C. to about 240 ° C., and a pressure in the range of about 500 to about 5,000 psi, and in the range of about 180 ° C. to about 220 ° C. And a pressure within the range of about 1,000 to about 2,500 psi is preferred.

  Any suitable hydrogenation catalyst can be used, such as described in US Pat. No. 3,654,370, the contents of which are incorporated by reference. In some embodiments, the hydrogenation catalyst is iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum mixed with one or more metals of group VIB of the periodic table, such as chromium, molybdenum or tungsten. And may comprise one or more metals from group VIIIB of the periodic table. Accelerators from Group IB of the periodic table such as copper can also be included. As an example, from about 60 mole percent to about 85 mole percent nickel, from about 14 mole percent to about 37 mole percent copper and about 60 mole percent nickel, such as a catalyst of the type disclosed in US Pat. No. 3,152,998. A catalyst comprising 1 mole percent to about 5 mole percent chromium (as chromium oxide) can be used. As another example, disclosed in U.S. Pat. No. 4,014,933, comprising about 70% to about 95% cobalt and nickel mixture and about 5% to about 30% iron by weight. A type of catalyst can be used. Another example is disclosed in US Pat. No. 4,152,353 comprising a third component that can be nickel, copper, and iron, zinc, zirconium or mixtures thereof. Types of catalysts, such as about 20% to about 49% nickel, about 36% to about 79% copper and about 1% to about 15% iron, zinc, zirconium or mixtures thereof. Containing catalysts can be used. As yet another example, a catalyst of the type described in US Pat. No. 4,766,245 comprising about 60% to about 75% nickel and about 25% to about 40% aluminum by weight Can be used.

  The reductive amination is preferably a continuous mixture in which a mixture of alkoxylated polyol, ammonia and hydrogen is continuously charged into a reactor containing a fixed bed of reductive amination catalyst and the reaction product is continuously withdrawn. Based on the principle.

  The reaction product is depressurized to recover excess hydrogen and ammonia for reuse and then fractionated to remove by-product reaction water and provide the desired etheramine mixture.

In carrying out the reductive amination, the reductive amination conditions to be used suitably include the use of about 4 moles to about 150 moles of ammonia per hydroxyl equivalent of the precursor polyol feedstock. it can. Hydrogen is preferably used in amounts of hydrogen ranging from about 0.5 molar equivalents to about 10 molar equivalents per hydroxyl equivalent of alkoxylated polyol feedstock. When the reaction is carried out on a batch principle, the contact time in the reaction zone is suitably in the range of about 0.1 hours to about 6 hours, and more preferably about 0.15 hours to about 2 hours. Can be within.

  When the reaction is carried out on a continuous basis using catalyst pellets, the reaction rate is suitably about 0.1 grams to about 2 grams of feedstock per hour per cubic meter of catalyst, More preferably, there can be about 0.3 grams to about 1.6 grams of feedstock per hour per cubic centimeter of catalyst.

  Further, the reductive amination is in the presence of from about 1 mole to about 200 moles of ammonia per mole of alkoxylated polyol, and more preferably from about 4 moles to about 130 moles of ammonia per mole of alkoxylated polyol. Can be implemented. From about 0.1 mole to about 50 moles of hydrogen per mole of alkoxylated polyol and more preferably from about 1 mole to about 25 moles of hydrogen per mole of alkoxylated polyol can be used.

  Some implementations described herein are of formula (IV):

To a composition comprising an ether amine.

In formula (IV), R ₃ and R ₄ may be the same or different and are each independently of the other hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl, may be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. m and n may each be an integer other than 0. m and n can each individually be a number from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6 when at least one of m and n is equal to or greater than 1. . m + n can be a number between 1 and 12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

  Some implementations described herein may be represented by formula (V):

To a composition comprising an ether amine.

In formula (V), R ₅ and R ₆ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group or a substituted or unsubstituted C ₆ -C ₁₂ aryl, can be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. m and n may each be an integer other than 0. m and n are each independently a number from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6, where at least one of m and n is equal to or greater than 1. m + n can be a number between 1 and 12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

  In some embodiments, the composition can further comprise at least one ether amine of formula (VI), formula (VII), and formula (VIII).

In formula (VI), R ₇ and R ₈ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group or a substituted or unsubstituted C ₆ -C ₁₂ aryl, can be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. x and y are each individually a number from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6 when at least one of x and y is 1 or more. x + y can be a number between 1 and 12, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

In formula (VII), R ₉ and R ₁₀ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group or a substituted or unsubstituted C ₆ -C ₁₂ aryl, can be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. x and y are each individually a number from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6 when at least one of x and y is 1 or more. x + y can be a number between 1 and 12, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

In formula (VIII), R ₁₁ and R ₁₂ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched. C ₂ -C ₅ alkenyl group or a substituted or unsubstituted C ₆ -C ₁₂ aryl, can be, for example CH _3, a C ₂ H ₅ or C ₆ H _5. x and y are each individually a number from 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6 when at least one of x and y is 1 or more. x + y can be a number between 1 and 12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

  In some implementations (etheramine derived from a first polyol initiator having a melting point above the processing temperature) / (ether amine derived from a second polyol initiator having a melting point below the processing temperature) The weight ratio is between 30:70 and 90:10. In some implementations, the composition is transparent and has a melting point of about 60 ° C. or less for ease of processing.

  According to some implementations, the composition is at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50% by weight, based on the total weight of the etheramine mixture. At least about 60 wt%, at least about 70 wt%, at least about 80 wt%, or at least about 90 wt% ether amine derived from a first polyol initiator having a melting point above the processing temperature. In other implementations, the etheramine mixture is about 10 wt% to about 90 wt%, about 20 wt% to about 80 wt%, about 30 wt% to about 70 wt%, based on the total weight of the etheramine mixture, It includes an ether amine derived from a first polyol initiator having a melting point above the processing temperature.

  In some implementations, the composition comprises an ether amine derived from a first polyol initiator having a melting point above the processing temperature of about 10% to about 90% by weight, based on the total weight of the ether amine mixture. And from about 90% to about 10% by weight of ether amine derived from a second polyol initiator having a melting point below the processing temperature, based on the total weight of the ether amine mixture.

  In yet another implementation, the present disclosure generally provides a composition comprising a polyurea material and a method for producing the same by reacting the ether amine mixture described herein with an organic polyisocyanate.

  In still other implementations, the present disclosure generally provides an epoxy resin-based composition and a composition thereof by contacting an etheramine mixture with an epoxy resin to form an epoxy resin system and curing the epoxy resin system. Provide recipes.

  Because of its favorable properties, the ether amine mixtures described herein can be used as a component in formulations that find use in a wide range of industrial applications, such as molding (resin casting). ), For the production of fiber-reinforced composites such as blades of wind turbine generators, for the production of tools, or for the production of coatings and / or intermediate coatings, the coatings and / or intermediate coatings being extensive Organic or inorganic substrates such as wood, wood fibers, natural or synthetic fabrics, plastics, glass, ceramics such as concrete, corrugated board, building materials such as artificial stone, eg iron Lies on a substrate such as a metal such as aluminum or copper. Furthermore, the etheramine mixtures described herein can be used as components of adhesives, cements, laminating resins, synthetic resin cements, paints or coatings. The formulation can be prepared before or during use, for example by contacting the components by mixing, and it can also be prepared by, for example, brushing, spraying, dip coating, extrusion, printing, electrostatic spraying, etc. It can be applied to one or more surfaces of any type and then subsequently cured to form a cured material.

  According to one implementation, the ether amine mixture of the present disclosure is contacted with an epoxy resin to form an epoxy resin formulation. The epoxy resin formulation can then be exposed to conditions sufficient to cure the epoxy resin formulation.

  The epoxy resin averages 1,2-epoxy equivalents of at least 1 epoxy group per molecule, preferably at least 1.3 epoxy groups per molecule and more preferably at least 1.6 epoxy groups per molecule. Any one reactive epoxy resin or mixture thereof with (functionality), and even more preferably, the mixture is polymerized to a useful material comprising an amine as described herein, or other It can be an epoxy resin with a functionality of at least 2 epoxy groups per molecule, which is believed to form its blend with an amine curing agent. In another embodiment, the epoxy resin has an average of at least 1.3 epoxy groups per molecule to about 8 epoxy groups per molecule, preferably at least about 1.6 epoxy groups per molecule to 1 molecule. Has a functionality in the range of about 5 epoxy groups per unit. Epoxy resins can be saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic, aromatic or heterocyclic and can carry substituents such as bromine or fluorine. . It may be a monomer or polymer, liquid or solid, but is preferably a liquid or low melting point solid at room temperature.

According to one implementation, the epoxy resin is a polyglycidyl epoxy compound, such as polyglycidyl ether, poly (β-methylglycidyl) ether, polyglycidyl ester or poly (β-methylglycidyl) ester. Polyglycidyl ether, poly (β-
The synthesis and examples of methyl glycidyl) ethers, polyglycidyl esters and poly (β-methyl glycidyl) esters are described in US Pat. No. 5,972,563, which is hereby incorporated by reference. Is disclosed. For example, an ether reacts a suitably substituted epichlorohydrin with a compound having at least one free alcoholic hydroxyl group and / or phenolic hydroxyl group under alkaline conditions or in the presence of an acidic catalyst, It can be obtained by subsequent alkali treatment. Alcohols include, for example, ethylene glycol, diethylene glycol, and higher order poly (oxyethylene) glycol, propane-1,2-diol or poly (oxypropylene) glycol, propane-1,3-diol, butane-1,4. -Diol, poly (oxytetramethylene) glycol, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol-1,1,1-trimethylolpropane, bistri It can be acyclic alcohols such as methylolpropane, pentaerythritol and sorbitol. However, suitable glycidyl ethers are also alicyclic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclo-hexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane. Or can be obtained from 1,1-bis (hydroxymethyl) cyclohexyl-3-ene or they can be N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) It can have an aromatic ring such as diphenylmethane.

  Representative examples of polyglycidyl ethers or poly (β-methyl glycidyl) ethers are those based on monocyclic phenols (eg resorcinol or hydroquinone), those based on polycyclic phenols (eg bis (4-hydroxy Phenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) S (bisphenol S), alkoxylated bisphenol A, F or S, triol chain extension Based on bisphenol A, F or S and brominated bisphenol A, F or S, hydrogenated bisphenol A, F or S, phenol and glycidyl ether of phenol with side groups or side chains, phenol novolac and Rezorunoboraku like, including formaldehyde and phenol or cresol obtained under acid conditions, those based on condensation products, or those based on a siloxane diglycidyl, a.

  Polyglycidyl esters and poly (β-methylglycidyl) esters can be produced by reacting epichlorohydrin or glycerol dichlorohydrin or β-methylepichlorohydrin with a polycarboxylic acid compound. The reaction is conveniently carried out in the presence of a base. The polycarboxylic acid compound can be, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid. However, it is also possible to use alicyclic polycarboxylic acids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid. Furthermore, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid can also be used, or for example trimellitic acid and polyols (eg glycerol or 2,2-bis ( A carboxyl-terminated adduct of 4-hydroxycyclohexyl) propane) can be used.

In other implementations, the epoxy resin is a non-glycidyl epoxy compound. Non-glycidyl epoxy compounds can be linear, branched or cyclic structures. For example, one or more epoxy compounds in which the epoxy group forms part of an acyclic or heterocyclic ring system can be included. Others include an epoxy-containing compound having at least one epoxycyclohexyl group bonded directly or indirectly to a group containing at least one silicon atom. An example is disclosed in US Pat. No. 5,639,413, which is hereby incorporated by reference. Still others include epoxy compounds containing one or more cyclohexene oxide groups and epoxy compounds containing one or more cyclopentene oxide groups. Particularly suitable non-glycidyl epoxy compounds are the following divalent non-glycidyl epoxy compounds in which the epoxy group forms part of an acyclic or heterocyclic ring system: bis (2,3-epoxycyclopentyl) ether, 1, 2-bis (2,3-epoxycyclopentyloxy) ethane, 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl 3,4-epoxy-6 -Methylcyclohexanecarboxylate, di (3,4-epoxycyclohexylmethyl) hexanedioate, di (3,4-epoxy-6-methylcyclohexylmethyl) hexanedioate, ethylenebis (3,4-epoxycyclohexanecarboxylate) Ethanediol di (3,4-epoxy (Cicyclohexylmethyl) ether, vinylcyclohexene dioxide, dicyclopentadiene diepoxide or 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-1,3-dioxane and 2,2 '-Bis (3,4-epoxy-cyclohexyl) -propane.

  In other implementations, the epoxy resin is preferably a resinous condensation of an aldehyde such as formaldehyde with either a monohydric phenol or a polyhydric phenol, in the presence of a basic catalyst such as sodium hydroxide or potassium hydroxide. It is an epoxy novolac compound obtained by reaction of a product with an epihalohydrin such as epichlorohydrin.

  In other implementations, the epoxy resin is a poly (N-glycidyl) compound or a poly (S-glycidyl) compound. The poly (N-glycidyl) compound is obtained, for example, by dehydrochlorination of a reaction product of an amine containing at least two amine hydrogen atoms and epichlorohydrin. These amines can be, for example, n-butylamine, aniline, toluidine, m-xylenediamine, bis (4-aminophenyl) methane or bis (4-methylaminophenyl) methane. Other examples of poly (N-glycidyl) compounds include N, N′-diglycidyl derivatives of cycloalkylene ureas such as ethylene urea or 1,3-propylene urea, and hydantoin N such as 5,5-dimethylhydantoin. , N′-diglycidyl derivatives. An example of a poly (S-glycidyl) compound is a di-S-glycidyl derivative derived from a dithiol (eg, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether).

  Epoxy-containing compounds in which the 1,2-epoxy groups are bonded to different heteroatoms or functional groups can also be used. Examples of these compounds are N, N, O-triglycidyl derivatives of 4-aminophenol, glycidyl ether / glycidyl ester of salicylic acid, N-glycidyl-N ′-(2-glycidyloxypropyl) -5,5-dimethyl. Hydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.

  Vinylcyclohexene dioxide, limonene dioxide, limonene monooxide, vinylcyclohexene monooxide, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxy-6-methyl cyclohexylmethyl 9,10-epoxystearate and 1,1 Other epoxy derivatives such as 2-bis (2,3-epoxy-2-methylpropoxy) ethane can be used. The use of pre-reacted adducts of oxetanes or liquids of epoxy-containing compounds such as those described above containing a curing agent for epoxy resins is also conceivable.

Epoxy resin blends are further added to conventional additives and adjuvants such as stabilizers, modifiers (m
modifiers), antifoaming agents, reinforcing agents, accelerators, co-curing agents, leveling agents, thickening agents, flame retardants, antioxidants, pigments, dyes, fillers and combinations thereof. be able to. For example, accelerators such as guanidine or its derivatives can be used in the epoxy resin formulation. Examples of guanidine derivatives include, but are not limited to, alkyl guanidines such as dimethyl guanidine or tetramethyl guanidine, or guanidinium salts derived from any of these. Examples of guanidinium salts include, but are not limited to, guanidine carbonate, guanidine acetate and guanidine nitrate. With the benefit of this disclosure, one of ordinary skill in the art would be able to identify suitable additives and adjuvants for use in the examples described herein.

  In some implementations described herein, the ether amine mixture may not require the use of a co-curing agent such as an alicyclic diamine (such as isophorone diamine). In these examples, it is believed that less material is required to produce the epoxy resin and less energy is required to reach a lower cure temperature.

  Once formulated, the epoxy resin formulation is applied to one or more surfaces by, for example, brushing, spraying, dipping, electrostatic spraying, etc., and exposed to appropriate conditions to cure the epoxy resin system. be able to. In one implementation, the epoxy resin formulation is cured under ambient conditions. In other implementations, the epoxy resin formulation is cured at elevated temperatures, such as at temperatures in the range of about 40 ° C to about 220 ° C. In some implementations of the present disclosure, lower and / or shorter cure temperatures than are typically required for modern epoxy resin systems in order to reach desired cure properties such as glass transition temperature. Time may be required. Achieving improved curing property generation at lower curing temperatures (such as baking) and / or shorter curing times can result in potential savings in energy costs and possible reduction in manufacturing process time ( Increased productivity). In the practice of this disclosure, the temperatures used for curing can be about 40 ° C., 45 ° C., 50 ° C., 55 ° C., 60 ° C. and 65 ° C. or less. In some implementations of the present disclosure, the curing time is about 2 hours, including intervals of about 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours and 5.5 hours ( hrs) to about 6 hours. In one embodiment of the present disclosure, the epoxy resin system is cured at about 55 ° C. for about 3 to about 6 hours. Those of skill in the art will appreciate how to achieve the desired cure characteristics using lower temperatures and / or shorter cure times, thanks to the present disclosure.

  In yet another implementation, the ether amine mixture of the present disclosure is reacted with an organic polyisocyanate to form a polyurea. Organic polyisocyanates include standard isocyanate compounds and compositions known to those skilled in the art. Suitable examples include quasi-prepolymers based on MDI-, such as those commercially available as RUBINATE (R) 9480, RUBINATE (R) 9484 and RUBINATE (R) 9495 brand products, all available from Huntsman International, LLC. Including. Liquefied MDI, such as MONDURU® ML isocyanate, available from Bayer MaterialScience, can also be used as all or part of the isocyanate.

Other organic polyisocyanates that can be used include those generally known to those skilled in the art. Thus, they can include, for example, aliphatic isocyanates of the type described in US Pat. No. 4,748,192. Accordingly, they are typically aliphatic diisocyanates, and more specifically trimerized or biuret forms of aliphatic diisocyanates such as hexamethylene diisocyanate, or tetraalkyls such as tetramethylxylene diisocyanate. It is a bifunctional monomer of xylene diisocyanate. Another example of an aliphatic isocyanate is cyclohexane diisocyanate. Other useful aliphatic isocyanates are described in US Pat. No. 4,705,814, which is hereby incorporated by reference in its entirety. They include aliphatic diisocyanates, for example, alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene group, such as 1,12-dodecane diisocyanate and 1,4-tetramethylene diisocyanate. In addition, 1,3- and 1,4-cyclohexane diisocyanate, and any desired mixture of these isomers, l-isocyanato-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophorone diisocyanate) Cycloaliphatic diisocyanates such as 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding mixture of isomers are also described.

  A wide range of aromatic polyisocyanates can also be used to form the polyureas of the present disclosure. Typical aromatic polyisocyanates are p-phenylene diisocyanate, polymethylene polyphenylisocyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate, vitorylene diisocyanate, naphthalene-1,4-diisocyanate, bis (4-isocyanate). Natophenyl) methane, bis (3-methyl-3-isocyanatophenyl) methane, bis (3-methyl-4-isocyanatophenyl) methane and 4,4′-diphenylpropane diisocyanate. Other aromatic polyisocyanates that can be used are methylene bridged polyphenyl polyisocyanate mixtures having a functionality of about 2 to about 4. These latter isocyanate compounds are generally produced conventionally by the reaction of formaldehyde with a primary aromatic amine (such as aniline) in the presence of hydrochloric acid and / or other acidic catalysts. Produced by phosgenation of the corresponding methylene bridged polyphenylpolyamine. Known methods for preparing polyamines and the corresponding methylene-bridged polyphenyl polyisocyanates therefrom are said to be incorporated herein by reference in the literature and in numerous patents, for example, U.S. Pat. Nos. 2,683,730, 2,950,263, 3,012,008, 3,344,162 and 3,362,979. Typically, the methylene bridged polyphenyl polyisocyanate mixture contains about 20 to about 100 weight percent of methylene diphenyl diisocyanate isomer, with the remainder being polymethylene polyphenyl diisocyanate with higher functionality and higher molecular weight. Polyphenyl polyisocyanate mixtures containing about 20 to about 100 weight percent diphenyl diisocyanate isomers are typical of these, of which about 20 to about 95 weight percent are 4,4′-isomers, with the remainder Is a functional polymethylene polyphenyl polyisocyanate having a higher molecular weight and an average functionality of about 2.1 to about 3.5. These isocyanate mixtures are known commercial materials and can be prepared by the methods described in US Pat. No. 3,362,979. A preferred aromatic polyisocyanate is methylene bis (4-phenyl isocyanate) or “MDI”. Pure MDI, quasi-prepolymer of MDI, modified pure MDI, etc. are useful for preparing polyureas according to the present invention. Since pure MDI is a solid and is therefore often inconvenient to use, liquid products based on MDI or methylenebis (4-phenylisocyanate) are used herein. US Pat. No. 3,394,164, which is hereby incorporated by reference, describes a liquid MI product. More generally, uretonimine modified pure MDI is also included. This product is produced by heating pure distilled MDI in the presence of a catalyst. The liquid product is a mixture of pure and modified MDI. The term organic polyisocyanate also includes quasi-prepolymers of isocyanates or polyisocyanates containing active hydrogen-containing materials.

  The following non-limiting examples are provided to more specifically illustrate the embodiments described herein. However, the examples are not intended to be exhaustive and are not intended to limit the scope of the embodiments described herein.

To a dry, nitrogen purged reactor was added 3175 grams of neopentyl glycol, 794 grams of ethylene glycol and 14.85 grams of KOH flakes. Next, 5186 grams of 1,2-butylene oxide was slowly added to the diol mixture with stirring. The reactor was then heated to 125 ° C. and temperature control was started. The reactor was then maintained at 125 ° C. for several hours. The diol mixture was then digested to steady pressure (digested).
down). Unreacted oxide was stripped. A certain amount of DI water and magnesium silicate (ie, Magnesol®) was then added to the diol mixture and digested at 120 ° C. for 2 hours. The reaction mixture was then stripped for about 1 hour at 50 mm Hg to remove any light reactants and water, and then the filtered product was recovered. The final alkoxylated polyol mixture had a hydroxyl number of 523 and a moisture content of <0.01%. The average molecular weight of the final alkoxylated polyol mixture was 215.

  To a dry, nitrogen purged reactor was added 3175 grams of neopentyl glycol, 794 grams of ethylene glycol and 13.21 grams of KOH flakes. Next, 4173 grams of propylene oxide was slowly added to the diol mixture with stirring. The reactor was then heated to 120 ° C. and temperature control was started. The reactor was then maintained at 120 ° C. for several hours. The diol mixture was then digested down to steady pressure. Unreacted oxide was stripped. A certain amount of DI water and magnesium silicate (ie, Magnesol®) was then added to the diol mixture and digested at 120 ° C. for 2 hours. The reaction mixture was then stripped for about 1 hour at 50 mm Hg to remove any light reactants and water, and then the filtered product was recovered. The final alkoxylated polyol mixture had a hydroxyl number of 571 and a moisture content of about 0.08%. The average molecular weight of the final alkoxylated polyol mixture was 197.

To a dry, nitrogen purged reactor was added 3402 grams of neopentyl glycol, 1458 grams of 1,4-butanediol and 14.28 grams of KOH flakes. Next, 3939 grams of propylene oxide was slowly added to the diol mixture with stirring. The reactor was then heated to 120 ° C. and temperature control was started. The reactor was then maintained at 120 ° C. for several hours. The diol mixture was then digested to steady pressure (digested).
down). Unreacted oxide was stripped. A certain amount of DI water and magnesium silicate (ie, Magnesol®) was then added to the diol mixture and digested at 120 ° C. for 2 hours. The reaction mixture was then stripped for about 1 hour at 50 mm Hg to remove any light reactants and water, and then the filtered product was recovered. The final alkoxylated polyol mixture had a hydroxyl number of 631 and a moisture content of 0.05%. The average molecular weight of the final alkoxylated polyol mixture was 178.

To a dry, nitrogen purged reactor was added 3175 grams of neopentyl glycol, 1361 grams of cyclohexanedimethanol and 12.95 grams of KOH flakes. Next, 3447 grams of propylene oxide was slowly added to the diol mixture with stirring. The reactor was then heated to 120 ° C. and temperature control was started. The reactor was then maintained at 120 ° C. for several hours. The diol mixture was then digested down to steady pressure. Unreacted oxide was stripped. A certain amount of DI water and magnesium silicate (ie, Magnesol®) was then added to the diol mixture and digested at 120 ° C. for 2 hours. The reaction mixture was then stripped for about 1 hour at 50 mm Hg to remove any light reactants and water, and then the filtered product was recovered. The final alkoxylated polyol mixture had a hydroxyl number of 560 and a moisture content of <0.01%. The average molecular weight of the final alkoxylated polyol mixture was 200.

  Each of the alkoxylated polyol mixtures was then aminated by reduction with ammonia to prepare the corresponding amine in a 100 cc continuous unit containing a fixed bed nickel-based catalyst. Polyol and ammonia were pumped separately, mixed in-line with hydrogen and fed into the catalyst bed. The polyol and ammonia were maintained at about 1: 1 weight feed ratio while maintaining a molar ratio of ammonia to hydrogen at about 10-20: 1 weight feed ratio. The reactor pressure was maintained at 2,000 psig during the total reductive amination process and the temperature was maintained at about 180-220 ° C. The polyol and ammonia feed rates used in each experiment varied between 65 g / hr and 100 g / hr. The product was recovered and stripped of excess ammonia, water and light amines.

  Table 1 represents the melting kinetics of selected alcohol mixtures, each mixture comprising low and high melting point alcohols mixed to form a low melting point mixture for ease of processing.

An epoxy resin formulation comprising a bisphenol A / F based epoxy resin having an epoxy equivalent weight of 169 was prepared using the ether amine mixture of Examples 1-4 as well as a commercially available curing agent (JEFFAMINE® D-230. Amine). The epoxy resin and amine curing agent were mixed in the amounts listed in Table 2 below to form an epoxy-based formulation and then cured under the conditions listed in Table 2. Then the glass transition temperature of the cured material (T _g), using a differential scanning calorimeter (DSC), and measured by selecting a temperature at the inflection point of a change in heat capacity as Tg. The results are shown in Table 2 below. In general, high melting point alcohols have a hard or hindered structure that results in enhanced thermal or mechanical properties. Based on the technical field of this patent, it is believed that alcohol raw materials with high melting points can be processed at low temperatures to save energy and improve properties.

  While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, the scope of which is determined by the following claims The

Claims (36)

(A) mixing a first polyol initiator having a melting point higher than the processing temperature and a second polyol initiator having a melting point lower than the processing temperature to form a polyol initiator mixture having a melting point lower than the processing temperature; Process,
(B) filling the alkoxylation reaction zone with a polyol initiator mixture in the presence of an alkali metal hydroxide catalyst;
(C) contacting the polyol initiator mixture with an alkylene oxide in the alkoxylation reaction zone to provide a mixture of alkoxylation precursor polyols; and (d) reducing the alkoxylation precursor polyol mixture to a reductive amination zone. And reductively aminating the mixture of alkoxylated precursor polyols in the presence of a reductive amination catalyst and ammonia to form an ether amine mixture:
A process for preparing an etheramine mixture comprising: The ether amine mixture is of formula (I)

[Wherein L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene, and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene, Preferably C ₄ -C ₈ cycloalkylene, and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene and preferably C ₂ -C ₄ alkylene-C ₅ -C ₆ cycloalkylene; C ₂ -C ₄ alkylene -C ₃ -C ₁₂ cycloalkylene -C ₂ -C ₄ alkylene and preferably at C ₂ -C ₄ alkylene -C ₅ -C ₆ cycloalkylene -C ₂ - C ₄ alkylene,
R ₃ and R ₄ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ -C ₅ alkenyl. Or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and m and n are each independently a number from 0 to 6 when at least one of m and n is 1 or more. Can be]
The process of claim 1 comprising the etheramine of The ether amine mixture is of formula (I)

[Wherein R ₁ and R ₂ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and m + n is equal to a non-zero integer between 1 and 6]
The process of claim 1 comprising the etheramine of The etheramine mixture further

[Wherein R ₃ and R ₄ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is a non-zero integer between 1 and 6],

[Wherein R ₅ and R ₆ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is a non-zero integer between 1 and 6], and

[Wherein R ₇ and R ₈ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is a non-zero integer between 1 and 6]:
The method of claim 3 comprising at least one of the following:   The process of claim 1 wherein the first polyol initiator is neopentyl glycol.   6. The method of claim 5, wherein the second polyol initiator is selected from the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol, ethylene glycol, and combinations thereof.   6. The method of claim 5, wherein the alkylene oxide is selected from the group consisting of propylene oxide, butylene oxide, ethylene oxide, and combinations thereof.   The process of claim 1 wherein the melting point of the second polyol initiator mixture is below 60 ° C and the melting point of the first polyol initiator is above 60 ° C.   The method of claim 8, wherein the melting point of the first polyol initiator is higher than 100C.   The process of claim 1 wherein the weight ratio of the first polyol initiator / second polyol initiator is between 30:70 and 90:10. Furthermore,
(E) contacting the etheramine mixture with the epoxy resin to form an epoxy resin system; and (f) curing the epoxy resin system:
The method of claim 1 comprising: Furthermore,
(E) reacting an etheramine mixture with an organic polyisocyanate to produce polyurea:
The method of claim 1 comprising:   A polyurea produced by the method of claim 12.   The method of claim 1, wherein the first polyol initiator is a solid and the second polyol initiator is a liquid.   15. The method of claim 14, wherein the polyol initiator mixture is a liquid. A composition comprising an ether amine mixture comprising a reaction product of ammonia and a mixture of alkoxylated precursor polyols,
The reaction is then carried out under reductive amination reaction conditions,
A mixture of alkoxylated polyols is a reaction product of a polyol initiator mixture having a melting point below the processing temperature and an alkylene oxide, and the polyol initiator mixture is a first polyol initiator having a melting point above the processing temperature; and Comprising a second polyol initiator having a melting point below the processing temperature:
Composition. The ether amine mixture has the formula (I):

[Wherein L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene, preferred Are C ₄ -C ₈ cycloalkylene and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene and preferably C ₂ -C ₄ alkylene-C _5-. C ₆ cycloalkylene; C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₂ -C ₄ alkylene and preferably C ₂ -C ₄ alkylene-C ₅ -C ₆ cycloalkylene-C ₂ -C ₄ Is alkylene;
R ₃ and R ₄ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ -C ₅ alkenyl. Or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and when at least one of m and n is 1 or more, m and n are each independently a number from 0 to 6 Can do]
17. The composition of claim 16 comprising the etheramine. The ether amine mixture has the formula (I):

[Wherein R ₅ and R ₆ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ A —C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and m + n is equal to a non-zero integer between 1 and 6]
17. The composition of claim 16 comprising the etheramine. The ether amine mixture is further

[Wherein R ₇ and R ₈ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6];

[Wherein R ₉ and R ₁₀ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6];

[Wherein R ₁₁ and R ₁₂ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6]:
19. The composition of claim 18, comprising at least one of the following.   17. The composition of claim 16, wherein the second polyol initiator is neopentyl glycol.   21. The composition of claim 20, wherein the second polyol initiator is selected from the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol, ethylene glycol, and combinations thereof.   21. The composition of claim 20, wherein the alkylene oxide is selected from the group consisting of: propylene oxide, butylene oxide, ethylene oxide, and combinations thereof.   The composition of claim 16, wherein the melting point of the first polyol initiator mixture is lower than 60C and the melting point of the second polyol initiator is higher than 60C.   24. The composition of claim 23, wherein the second polyol initiator has a melting point greater than 100 <0> C.   The composition of claim 16, wherein the weight ratio of the first polyol initiator / second polyol initiator is between 30:70 and 90:10.   26. The composition of claim 25, wherein the composition is transparent and has a melting point of 60 [deg.] C or less.   17. The composition of claim 16, wherein the composition is a polyurea composition.   17. The composition of claim 16, wherein the composition is an epoxy resin system.   17. The composition of claim 16, wherein the first polyol initiator is a solid and the second polyol initiator is a liquid.   30. The composition of claim 29, wherein the polyol initiator mixture is a liquid.

[L is linear or branched C ₂ -C ₁₈ alkylene, preferably C ₂ -C ₁₂ alkylene and particularly preferably C ₂ -C ₆ alkylene; C ₃ -C ₁₂ cycloalkylene, preferably C ₄ -C ₈ cycloalkylene and particularly preferably C ₅ -C ₈ cycloalkylene; C ₂ -C ₄ alkylene -C ₃ -C ₁₂ cycloalkylene and preferably at C ₂ -C ₄ alkylene -C ₅ -C ₆ cycloalkylene C ₂ -C ₄ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₂ -C ₄ alkylene and preferably C ₂ -C ₄ alkylene-C ₅ -C ₆ cycloalkylene-C ₂ -C ₄ alkylene;
R ₃ and R ₄ may be the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ -C ₅ alkenyl. Or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and when at least one of m and n is 1 or more, m and n are each independently a number from 0 to 6 be able to]:
A composition comprising.

[Wherein R ₅ and R ₆ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and m + n is equal to a non-zero integer between 1 and 6]:
A composition comprising The composition further comprises

[Wherein R ₇ and R ₈ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6];

[Wherein R ₉ and R ₁₀ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6];

[Wherein R ₁₁ and R ₁₂ are the same or different and are each independently of one another hydrogen, linear or branched C ₁ -C ₅ alkyl group, linear or branched C ₂ — A C ₅ alkenyl group, or a substituted or unsubstituted C ₆ -C ₁₂ aryl group, and x + y is equal to a non-zero integer between 1 and 6]:
33. The composition of claim 32, comprising at least one of the following. From about 10% to about 90% by weight of the ether amine of formula (I), based on the total weight of the composition, and from about 10% to about 90% by weight, based on the total weight of the composition, of formula (II), formula At least one ether amine of formula (III) and formula (IV):
34. The composition of claim 33, comprising:   35. The composition of claim 32, wherein the composition is a polyurea composition.   33. The composition of claim 32, wherein the composition is an epoxy resin system.